U.S. patent application number 16/570300 was filed with the patent office on 2020-01-02 for magnetoresistance effect element.
This patent application is currently assigned to TDK CORPORATION. The applicant listed for this patent is TDK CORPORATION. Invention is credited to Tomoyuki SASAKI.
Application Number | 20200006640 16/570300 |
Document ID | / |
Family ID | 61686724 |
Filed Date | 2020-01-02 |
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United States Patent
Application |
20200006640 |
Kind Code |
A1 |
SASAKI; Tomoyuki |
January 2, 2020 |
MAGNETORESISTANCE EFFECT ELEMENT
Abstract
A magnetoresistance effect element has favorable symmetry of an
MR ratio even if the sign of a bias voltage is different, which is
capable of reversing magnetization to a current, which has a high
MR ratio. A magnetoresistance effect element includes a laminate in
which an underlayer, a first ferromagnetic metal layer, a tunnel
barrier layer, and a second ferromagnetic metal layer are laminated
in that order. The underlayer is made of one or more selected from
a group containing of TiN, VN, NbN, and TaN, or mixed crystals
thereof. The tunnel barrier layer is made of a compound having a
spinel structure and represented by the following composition
formula (1): A.sub.xGa.sub.2O.sub.y, where A is a non-magnetic
divalent cation and represents a cation of at least one element
among magnesium, zinc, and cadmium, x is a number satisfying
0<x.ltoreq.2, and y is a number satisfying 0<y.ltoreq.4.
Inventors: |
SASAKI; Tomoyuki; (Tokyo,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
TDK CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
TDK CORPORATION
Tokyo
JP
|
Family ID: |
61686724 |
Appl. No.: |
16/570300 |
Filed: |
September 13, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
15716094 |
Sep 26, 2017 |
10454022 |
|
|
16570300 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
G11C 11/161 20130101;
H01L 43/02 20130101; H01L 43/10 20130101; H01L 43/08 20130101; H01L
27/222 20130101 |
International
Class: |
H01L 43/02 20060101
H01L043/02; H01L 43/10 20060101 H01L043/10; G11C 11/16 20060101
G11C011/16; H01L 43/08 20060101 H01L043/08 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 29, 2016 |
JP |
2016-192009 |
Claims
1. A magnetoresistance effect element comprising a laminate in
which: an underlayer; a first ferromagnetic metal layer; a tunnel
barrier layer, and a second ferromagnetic metal layer are laminated
in this order, wherein the underlayer is made of one or more
selected from a group consisting of TiN, VN, NbN, and TaN, and the
tunnel barrier layer is made of a compound having a spinel
structure and represented by a composition formula (1) below,
A.sub.xGa.sub.2O.sub.y (1): where A is a non-magnetic divalent
cation and represents a cation of at least one element selected
from a group consisting of magnesium, zinc, and cadmium, x is a
number that satisfies 0<x.ltoreq.2, and y is a number that
satisfies 0<y.ltoreq.4, wherein the tunnel barrier layer has a
spinel structure in which an atomic arrangement is disordered.
2. The magnetoresistance effect element according to claim 1,
wherein A in the composition formula (1) is a cation of at least
one element selected from a group consisting of magnesium and zinc,
and the underlayer is made of mixed crystals of one or more
selected from a group consisting of TiN, VN, and TaN.
3. The magnetoresistance effect element according to claim 1,
wherein A in the composition formula (1) is a cadmium ion, and the
underlayer is made of NbN.
4. The magnetoresistance effect element according to claim 3,
wherein the tunnel barrier layer comprises: a lattice-matched
portion that lattice-matches with both of the first ferromagnetic
metal layer and the second ferromagnetic metal layer; and a
non-lattice-matched portion that is free of a lattice-matching with
at least one of the first ferromagnetic metal layer and the second
ferromagnetic metal layer.
5. The magnetoresistance effect element according to claim 1,
wherein the tunnel barrier layer has a spinel structure in which an
atomic arrangement is disordered.
6. The magnetoresistance effect element according to claim 1,
wherein a crystal lattice of either or both of the first
ferromagnetic metal layer and the second ferromagnetic metal layer
matches the tunnel barrier layer in a cubic-on-cubic structure.
7. The magnetoresistance effect element according to claim 2,
wherein a crystal lattice of either or both of the first
ferromagnetic metal layer and the second ferromagnetic metal layer
matches the tunnel barrier layer in a cubic-on-cubic structure.
8. The magnetoresistance effect element according to claim 3,
wherein a crystal lattice of either or both of the first
ferromagnetic metal layer and the second ferromagnetic metal layer
matches the tunnel barrier layer in a cubic-on-cubic structure.
9. The magnetoresistance effect element according to claim 4,
wherein a crystal lattice of either or both of the first
ferromagnetic metal layer and the second ferromagnetic metal layer
matches the tunnel barrier layer in a cubic-on-cubic structure.
10. The magnetoresistance effect element according to claim 5,
wherein a crystal lattice of either or both of the first
ferromagnetic metal layer and the second ferromagnetic metal layer
matches the tunnel barrier layer in a cubic-on-cubic structure.
11. The magnetoresistance effect element according to claim 1,
wherein at least one of the first ferromagnetic metal layer and the
second ferromagnetic metal layer has magnetic anisotropy
perpendicular to a lamination direction.
12. The magnetoresistance effect element according to claim 2,
wherein at least one of the first ferromagnetic metal layer and the
second ferromagnetic metal layer has magnetic anisotropy
perpendicular to a lamination direction.
13. The magnetoresistance effect element according to claim 3,
wherein at least one of the first ferromagnetic metal layer and the
second ferromagnetic metal layer has magnetic anisotropy
perpendicular to a lamination direction.
14. The magnetoresistance effect element according to claim 4,
wherein at least one of the first ferromagnetic metal layer and the
second ferromagnetic metal layer has magnetic anisotropy
perpendicular to a lamination direction.
15. The magnetoresistance effect element according to claim 5,
wherein at least one of the first ferromagnetic metal layer and the
second ferromagnetic metal layer has magnetic anisotropy
perpendicular to a lamination direction.
16. The magnetoresistance effect element according to claim 1,
wherein at least one of the first ferromagnetic metal layer and the
second ferromagnetic metal layer is
Co.sub.2Mn.sub.1-aFe.sub.aAl.sub.bSi.sub.1-b (0.ltoreq.a.ltoreq.1,
0.ltoreq.b.ltoreq.1).
17. The magnetoresistance effect element according to claim 2,
wherein at least one of the first ferromagnetic metal layer and the
second ferromagnetic metal layer is
Co.sub.2Mn.sub.1-aFe.sub.aAl.sub.bSi.sub.1-b (0.ltoreq.a.ltoreq.1,
0.ltoreq.b.ltoreq.1).
18. The magnetoresistance effect element according to claim 3,
wherein at least one of the first ferromagnetic metal layer and the
second ferromagnetic metal layer is
Co.sub.2Mn.sub.1-aFe.sub.aAl.sub.bSi.sub.1-b (0.ltoreq.a.ltoreq.1,
0.ltoreq.b.ltoreq.1).
19. The magnetoresistance effect element according to claim 4,
wherein at least one of the first ferromagnetic metal layer and the
second ferromagnetic metal layer is
Co.sub.2Mn.sub.1-aFe.sub.aAl.sub.bSi.sub.1-b (0.ltoreq.a.ltoreq.1,
0.ltoreq.b.ltoreq.1).
20. The magnetoresistance effect element according to claim 5,
wherein at least one of the first ferromagnetic metal layer and the
second ferromagnetic metal layer is
Co.sub.2Mn.sub.1-aFe.sub.aAl.sub.bSi.sub.1-b (0.ltoreq.a.ltoreq.1,
0.ltoreq.b.ltoreq.1).
Description
[0001] This is a Continuation of application Ser. No. 15/716,094
filed Sep. 26, 2017, which in turn claims the benefit of Japanese
Patent Application No. 2016-192009, filed Sep. 29, 2016. The
disclosure of the prior applications is hereby incorporated by
reference herein in its entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The present invention relates to a magnetoresistance effect
element.
Description of Related Art
[0003] A giant magnetoresistance (GMR) element made of a multilayer
film including a ferromagnetic layer and a non-magnetic layer and a
tunnel magnetoresistance (TMR) element in which an insulating layer
(a tunnel barrier layer and a barrier layer) is used as a
non-magnetic layer are known (JP2012-60087A; JP5586028B,
JP2013-175615A; APPLIED PHYSICS LETTERS 96, 212505, (2010); Applied
Physics Letters, 105, 242407 (2014); and Physical Review B 86,
024426 (2012)). In general, the TMR element has a higher element
resistance than the GMR element, and the TMR element has a higher
magnetoresistance (MR) ratio than the GMR element. TMR elements can
be classified into two types. The first type is a TMR element that
uses only a tunneling effect which utilizes a leaching effect of a
wave function between ferromagnetic layers. The second type is a
TMR element that uses a coherent tunnel which utilizes conduction
of a specific orbital of a non-magnetic insulating layer to be
tunneled when the above tunneling effect is exhibited. It is known
that the TMR element using the coherent tunnel can obtain a higher
MR ratio than the TMR element using only the tunneling effect. This
coherent tunneling effect is exhibited when both of the
ferromagnetic layer and the non-magnetic insulating layer are
crystalline, and an interface between the ferromagnetic layer and
the non-magnetic insulating layer is crystallographically
continuous.
[0004] Magnetoresistance effect elements are used for various
applications. For example, as a magnetic sensor, a
magnetoresistance effect type magnetic sensor is known. In a hard
disk drive, a magnetoresistance effect element determines a
characteristic of a playback function.
[0005] The magnetoresistance effect type magnetic sensor is a
magnetic sensor configured to detect an effect of a change in a
magnetization direction of a magnetoresistance effect element due
to a magnetic field from the outside as a change in resistance of a
magnetoresistance effect element.
[0006] A device expected in the future is a magnetoresistance
change type random access memory (MRAM). The MRAM is a memory in
which directions of ferromagnetic magnetism of two layers are
appropriately changed to parallel or antiparallel and which reads a
magnetoresistance as a digital signal such as 0 or 1.
SUMMARY OF THE INVENTION
[0007] Writing of information using spin transfer torque (STT) is
drawing attention in the MRAM. This is because a current density at
which information can be written is applied to a magnetic element;
and information to be written can be determined according to a
direction of a current. However, a current or a voltage necessary
for rewriting information varies since the information is generally
rewritten by the direction of the current applied to the
magnetoresistance effect element, which is the polarity of the
voltage. Thus, there is a problem that ease of rewriting varies
depending on information.
[0008] One factor of the problem that ease of rewriting varies
depending on information is that the MR ratio varies depending on
the direction of the current that flows in the magnetoresistance
effect element. Using the STT, ease of rewriting is proportional to
the magnitude of the MR ratio. That is, when the MR ratio varies
depending on the direction of the current, the magnitude of the
current for rewriting information varies. Therefore, an element in
which the MR ratio does not depend on the direction of the current
bias (the symmetry of the MR ratio with respect to a current bias
is favorable), that is, a magnetoresistance effect element, is
required as an MRAM or a switch. In addition, when the
magnetoresistance effect element is used as a high frequency
oscillator or a wave detector, similarly, a magnetoresistance
effect element in which the MR ratio does not depend on the
direction of the current bias is required. In high frequency
applications, if the symmetry with respect to the current bias is
excellent, stability with respect to a frequency is improved.
[0009] As a material of a tunnel barrier layer capable of obtaining
the coherent tunneling effect, MgO is widely known. In
JP2012-60087A, JP5586028B and APPLIED PHYSICS LETTERS 96, 212505,
(2010), as a material of the tunnel barrier layer, an oxide having
a spinel structure is described. In JP2012-60087A, as examples of
the oxide having a spinel structure, MgAl.sub.2O.sub.4,
FeAl.sub.2O.sub.4, CoAl.sub.2O.sub.4, MgCr.sub.2O.sub.4, and
MgGa.sub.2O.sub.4 are named. In addition, it is described in
JP2013-175615A, Applied Physics Letters, 105, 242407 (2014), and
Physical Review B 86, 024426 (2012) that MgAl.sub.2O.sub.4 needs to
have a disordered spinel structure in order to obtain a high MR
ratio. The disordered spinel structure referred to here is a
structure in which O atoms are arranged to form a closely packed
cubic lattice which is substantially the same as that of a spinel,
but an atomic arrangement of Mg and Al is disordered, and is cubic
as a whole. In the original spinel, Mg and Al are regularly
arranged in tetrahedral voids and octahedral voids of oxygen ions.
However, in the disordered spinel structure, since these are
provided at random, the symmetry of crystals is changed, and a
structure has a lattice constant which is substantially reduced
from about 0.808 nm of MgAl.sub.2O.sub.4 by half is provided.
[0010] The purpose of the present invention is to provide a
magnetoresistance effect element which has more favorable symmetry
of an MR ratio with respect to the polarity of a bias voltage than
the conventional TMR element in which MgO and MgAl.sub.2O.sub.4 are
used as a material of the tunnel barrier layer. In the
magnetoresistance effect element, when a bias voltage is positive
and negative, the proportion of a change in the MR ratio according
to the change in an applied voltage value is the same. Moreover,
magnetization reversal by the current can be performed efficiently;
and a high MR ratio of the magnetoresistance effect element can be
obtained.
[0011] In order to address the above problem, a magnetoresistance
effect element according to the present invention has a laminate in
which: an underlayer; a first ferromagnetic metal layer; a tunnel
barrier layer, and a second ferromagnetic metal layer are laminated
in this order, wherein the underlayer is made of one or more
selected from a group consisting of TiN, VN, Nb, and TaN or mixed
crystal thereof, and the tunnel barrier layer is made of a compound
having a spinel structure and represented by a composition formula
(1) below.
A.sub.xGa.sub.2O.sub.y (1):
[0012] where A is a non-magnetic divalent cation and represents a
cation of at least one element selected from a group consisting of
magnesium, zinc, and cadmium, x is a number that satisfies
0<x.ltoreq.2, and y is a number that satisfies
0<y.ltoreq.4.
[0013] Since a spinel material containing gallium and oxygen shows
a symmetric MR ratio irrespective of the sign of a bias voltage,
the spin polarizability hardly attenuates in a low bias region.
Therefore, information can be rewritten with a lower voltage than
that in the related art.
[0014] Further, it is believed that the MR ratio further increases
because the underlayer is made of one or more selected from the
group consisting of TiN, VN, NbN, and TaN or, mixed crystals
thereof. Although the reason for this is not clear, the inventors
found that, when a difference between a crystal lattice constant of
a material constituting the tunnel barrier layer and a number
obtained by multiplying a crystal lattice constant that a nitride
constituting the underlayer has by n (n is a natural number or
1/natural number) is smaller, the MR ratio is larger. Therefore,
influence of the under layer on the crystallinity of the tunnel
barrier layer should be taken into account. This result contradicts
with the conventional wisdom. Generally, it is said that a nitride
film formed by a reactive sputtering method is amorphous.
Therefore, a TiN film, a VN film, an NbN film, and a TaN film
formed by the reactive sputtering method used in examples are
amorphous. However, when the underlayer is completely amorphous,
there is no crystallographic correlation with a layer thereabove,
and the result obtained by the inventors contradicts with the
conventional wisdom.
[0015] The reason for this is inferred to be as follows. Since no
atomic image is obtained even if the underlayer of the present
invention is observed through TEM, it cannot be said that the
underlayer is completely crystallized. On the other hand, the
underlayer cannot be said to be completely amorphous, and although
there is not an extent to obtain an atomic image through TEM, it is
believed that an image that locally includes a crystalline part may
be close to reality.
[0016] The present invention reveals new prospects for increasing
the MR ratio of the magnetoresistance effect element with respect
to a current state in which the nitride film formed by the reactive
sputtering method is amorphous.
[0017] Here, as will be described below in examples, the result can
be described by comparing a lattice mismatching degree obtained
from a crystal lattice constant that a nitride (TiN, VN, NbN, TaN,
and a mixed crystal thereof) constituting an underlayer of a
magnetoresistance effect element has and a lattice constant of a
tunnel barrier layer with the MR ratio. The crystal structure that
VN, TiN, and a mixed crystal thereof can have is generally a
tetragonal structure (NaCl structure) and is a crystal structure in
which a space group is Fm-3m. A crystal lattice constant of the
structure is disclosed in, for example, "AtomWork" (accessed on
Aug. 23, 2016, URL: http://crystdb.nims.go.jp/) provided by
National Institute for Materials Science (Japan).
[0018] Furthermore, since TiN, VN, NbN, and TaN have conductivity,
when an underlayer is made of such a nitride, a voltage can be
applied to the magnetoresistance effect element through the
underlayer, and the configuration of the element can be
simplified.
[0019] In the magnetoresistance effect element, A in the
composition formula (1) may be a cation of at least one element
selected from a group consisting of magnesium and zinc, and the
underlayer is made of one or more selected from a group consisting
of TiN, VN, and TaN, or mixed crystals thereof.
[0020] When the material constituting the underlayer and the
material constituting the tunnel barrier layer are combined as
above, a difference of lattice constants between the underlayer and
the tunnel barrier layer is further reduced and the MR ratio
further increases.
[0021] In the magnetoresistance effect element, A in the
composition formula (1) may be a cadmium ion, and the underlayer
may be made of NbN.
[0022] When the material constituting the underlayer and the
material constituting the tunnel barrier layer are combined as
above, a difference of lattice constants between the underlayer and
the tunnel barrier layer is further reduced and the MR ratio
further increases.
[0023] In the magnetoresistance effect element, the tunnel barrier
layer may include: a lattice-matched portion that lattice-matches
with both of the first ferromagnetic metal layer and the second
ferromagnetic metal layer; and a non-lattice-matched portion that
is free of a lattice-matching with at least one of the first
ferromagnetic metal layer and the second ferromagnetic metal
layer.
[0024] In the magnetoresistance effect element, the tunnel barrier
layer may have a spinel structure in which an atomic arrangement is
disordered.
[0025] When the spinel structure in which an atomic arrangement is
disordered is provided, the coherent tunneling effect is
strengthened due to an electronic band folding effect, and the MR
ratio increases.
[0026] In the magnetoresistance effect element, a crystal lattice
of either or both of the first ferromagnetic metal layer and the
second ferromagnetic metal layer may match the tunnel barrier layer
in a cubic-on-cubic structure.
[0027] A spinel material containing gallium and oxygen has a
cubic-on-cubic structure in which a ferromagnetic material such as
iron matches a crystal lattice. Therefore, since scattering at an
interface between the tunnel barrier layer and the ferromagnetic
metal layer is prevented, a bias dependency of the MR ratio shows a
symmetric structure irrespective of a direction of a voltage.
Therefore, information can be rewritten with a lower voltage than
that in the related art.
[0028] In the magnetoresistance effect element, coercivity of the
second ferromagnetic metal layer may be greater than coercivity of
the first ferromagnetic metal layer.
[0029] Since coercivity of the first ferromagnetic metal layer and
the second ferromagnetic metal layer are different from each other,
the element functions as a spin valve and can be applied for
devices.
[0030] In the magnetoresistance effect element, a magnetoresistive
ratio may be 100% or more under an application of a voltage of 1 V
or more at room temperature.
[0031] In a device to which a high bias voltage is applied such as
a high sensitivity magnetic sensor, a logic-in-memory, and an MRAM,
the magnetoresistance effect element can be used.
[0032] In the magnetoresistance effect element, at least one of the
first ferromagnetic metal layer and the second ferromagnetic metal
layer may have magnetic anisotropy perpendicular to a lamination
direction.
[0033] Since it is not necessary to apply a bias magnetic field, it
is possible to reduce the size of the device. In addition, since
the element has a high thermal disturbance resistance, it can
function as a recording element.
[0034] In the magnetoresistance effect element, at least one of the
first ferromagnetic metal layer and the second ferromagnetic metal
layer may be Co.sub.2Mn.sub.1-aFe.sub.aAl.sub.bSi.sub.1-b
(0.ltoreq.a.ltoreq.1, 0.ltoreq.b.ltoreq.1).
[0035] Co.sub.2Mn.sub.1-aFe.sub.aAl.sub.bSi.sub.1-b is a
ferromagnetic metal material having a high spin polarizability, and
it is possible to obtain a higher MR ratio compared to when another
ferromagnetic metal material is used.
[0036] According to the present invention, it is possible to
provide a magnetoresistance effect element which has more favorable
symmetry of an MR ratio with respect to the polarity of a bias
voltage than a TMR element in which MgO and MgAl.sub.2O.sub.4 are
used as a material of a tunnel barrier layer of the related art,
that is, when a bias voltage is positive and negative, the
proportion of a change in the MR ratio according to a change in an
applied voltage value is the same, and which is capable of
efficiently reversing magnetization according to a current, and has
a high MR ratio.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] FIG. 1 is an enlarged cross-sectional view of a main part
for explaining a laminated structure of a magnetoresistance effect
element according to an aspect of the present invention.
[0038] FIG. 2 is a schematic diagram of an example of a crystal
structure of a regular spinel constituting a tunnel barrier layer
of a magnetoresistance effect element according to an aspect of the
present invention.
[0039] FIG. 3 is a schematic diagram of an example of a crystal
structure of a disordered spinel constituting a tunnel barrier
layer of a magnetoresistance effect element according to an aspect
of the present invention.
[0040] FIG. 4 is a schematic diagram of another example of a
crystal structure of a disordered spinel constituting a tunnel
barrier layer of a magnetoresistance effect element according to an
aspect of the present invention.
[0041] FIG. 5 is a schematic diagram of still another example of a
crystal structure of a disordered spinel constituting a tunnel
barrier layer of a magnetoresistance effect element according to an
aspect of the present invention.
[0042] FIG. 6 is a schematic diagram of yet another example of a
crystal structure of a disordered spinel constituting a tunnel
barrier layer of a magnetoresistance effect element according to an
aspect of the present invention.
[0043] FIG. 7 is a schematic diagram of yet another example of a
crystal structure of a disordered spinel constituting a tunnel
barrier layer of a magnetoresistance effect element according to an
aspect of the present invention.
[0044] FIG. 8 is a plan view of a magnetoresistance effect device
including a magnetoresistance effect element according to an aspect
of the present invention.
[0045] FIG. 9 is a cross-sectional view taken along the line IX-IX
in FIG. 8.
[0046] FIG. 10 is an example of a portion in which a tunnel barrier
layer and a ferromagnetic metal layer are lattice-matched.
[0047] FIG. 11 is a structure diagram of a cross section having a
direction parallel to a lamination direction of a tunnel barrier
layer.
DETAILED DESCRIPTION OF THE INVENTION
[0048] Embodiments of the present invention will be described below
in detail with reference to the drawings. Here, in descriptions of
the drawings, the same components are denoted with the same
reference numerals and redundant descriptions will be omitted.
First Embodiment
[0049] A magnetoresistance effect element 100 according to a first
embodiment will be described below. The magnetoresistance effect
element 100 has a laminate in which an underlayer 2, a first
ferromagnetic metal layer 6, a tunnel barrier layer 3, and a second
ferromagnetic metal layer 7 are laminated in that order. The
underlayer 2 is made of TiN, VN, or a mixed crystal thereof. The
tunnel barrier layer 3 is made of a compound having a spinel
structure and represented by the following composition formula
(1).
A.sub.xGa.sub.2O.sub.y (1):
[0050] where, A is a non-magnetic divalent cation and represents a
cation of at least one element selected from the group consisting
of magnesium, zinc, and cadmium, x is a number that satisfies
0<x.ltoreq.2, and y is a number that satisfies
0<y.ltoreq.4
(Basic Structure)
[0051] In the example shown in FIG. 1, the magnetoresistance effect
element 100 is provided on a substrate 1 and has a structure in
which the underlayer 2, the first ferromagnetic metal layer 6, the
tunnel barrier layer 3, the second ferromagnetic metal layer 7, and
a cap layer 4 are laminated in that order from the substrate 1.
(Underlayer)
[0052] The underlayer 2 is made of one or more selected from the
group consisting of TiN, VN, NbN, and TaN or, mixed crystals
thereof. Here, the term "mixed crystals" is used for convenience of
description, and it does not mean that the underlayer 2 is
crystalline, but simply means that a film is formed of a
combination of two or more nitrides, and may refer to a mixed film
containing two or more nitrides. As examples of the mixed crystals,
a material containing TiN and VN, a material containing TiN and
TaN, TiN, and NbN can be exemplified. In addition, it is not
necessary for the metal nitride constituting the underlayer 2 to
have an atomic ratio between a metal element and N of 1:1. The
atomic ratio between a metal element and N is preferably in a range
of 1:0.5 to 1:2 (=metal element: N).
(Tunnel Barrier Layer)
[0053] The tunnel barrier layer 3 is made of a non-magnetic
insulating material. In general, a film thickness of the tunnel
barrier layer is 3 nm or less. When the tunnel barrier layer 3 is
interposed between metal materials, since a wave function of
electrons included in atoms of the metal materials spread beyond
the tunnel barrier layer 3, a current can flow although an
insulator is provided on a circuit. The magnetoresistance effect
element 100 has a structure in which the tunnel barrier layer 3 is
interposed between ferromagnetic metal materials, and a resistance
value is determined by a relative angle formed by magnetization
directions of sandwiching ferromagnetic metals. In the
magnetoresistance effect element 100, a general tunneling effect
and the coherent tunneling effect in which orbitals during
tunneling are limited are exhibited. In the general tunneling
effect, a magnetoresistance effect is obtained due to the spin
polarizability of a ferromagnetic material. On the other hand, in
coherent tunneling, since orbitals during tunneling are limited, a
greater effect than with the spin polarizability of a ferromagnetic
material can be expected. Therefore, in order for the coherent
tunneling effect to be exhibited, the ferromagnetic material and
the tunnel barrier layer 3 need to be crystallized and bonded in a
specific direction.
(Spinel Structure)
[0054] The non-magnetic insulating material constituting the tunnel
barrier layer 3 is a compound having a spinel structure and
represented by the composition formula (1). Here, in the present
embodiment, the spinel structure includes a regular spinel
structure and a spinel structure (regular spinel structure) in
which an atomic arrangement is disordered.
[0055] As shown in FIG. 2, the regular spinel structure refers to a
structure which includes an A site in which cations
tetra-coordinate with oxygen atoms and a B site in which cations
hexa-coordinate with oxygen atoms. In the structure, oxygen atoms
are arranged to form a closely packed cubic lattice, and the
structure is cubic as a whole. The disordered spinel structure
refers to a structure in which oxygen atoms are arranged to form a
closely packed cubic lattice which is substantially the same as
that in the regular spinel structure, but an atomic arrangement of
cations is disordered. That is, in the regular spinel structure,
cations are regularly arranged in tetrahedral voids and octahedral
voids of oxygen atoms. On the other hand, in the disordered spinel
structure, since cations are provided at random, the symmetry of
crystals is changed, and a lattice constant is substantially
reduced by half in the structure. For example, it is known that a
space group consisting of the regular spinel structure represented
by MgAl.sub.2O.sub.4 is Fd-3m, but a space group consisting of the
disordered spinel structure in which a lattice constant is reduced
by half is Fm-3m or F-43m. As the disordered spinel structure,
there are five possible structures in total shown in FIG. 3 to FIG.
7, and any one of these structures or a structure in which these
structures are mixed may be used. The disordered spinel structure
is called a Sukenel structure in some cases.
[0056] In addition, in the disordered spinel structure, when a unit
of lattice repetition is changed, a combination of a ferromagnetic
layer material and an electron structure (band structure) is
changed. Therefore, the disordered spinel structure shows greater
TMR enhancement due to the coherent tunneling effect than the
regular spinel structure. Thus, when the tunnel barrier layer 3 has
a disordered spinel structure, the coherent tunneling effect is
strengthened due to an electronic band folding effect and the MR
ratio increases.
[0057] Here, in the present embodiment, it is not essentially
needed for the disordered spinel structure to be cubic as a whole.
A crystal structure of the non-magnetic insulating material
constituting the tunnel barrier layer 3 is influenced by the
crystal structure of the underlying material, and the lattice is
partially distorted. Although such materials have a bulk crystal
structure, when a thin film is formed, a partially distorted
crystal structure based on a bulk crystal structure is taken.
[0058] In particular, in the present embodiment, the tunnel barrier
layer 3 is a very thin film, and is easily influenced by the
crystal structure of the layer in contact with the tunnel barrier
layer 3. However, in the material having the disordered spinel
structure, the bulk crystal structure is basically cubic. The
disordered spinel structure in the present embodiment includes a
structure slightly deviated from cubic even if it is not cubic. In
general, the deviation from the cubic in the disordered spinel
structure in the present embodiment is slight, and depends on
accuracy of the measurement method of evaluating the crystal
structure.
[0059] A divalent cation in non-magnetic elements contained in the
tunnel barrier layer 3, that is, A in the composition formula (1),
forms an A site of the spinel structure. The divalent cation that
forms the A site is a cation of at least one non-magnetic element
selected from the group consisting of magnesium, zinc, and cadmium.
Magnesium, zinc, and cadmium are stable in a divalent state, and
when they used as constituent elements of the tunnel barrier layer,
coherent tunneling can be realized and the MR ratio increases.
[0060] When divalent cations contained in the tunnel barrier layer
3 are derived from a plurality of types of non-magnetic element,
such divalent cations of a plurality of types of non-magnetic
element preferably have a small ionic radius difference that is 0.2
.ANG. or less. When the ionic radius difference is small, a cation
arrangement does not easily become ordered, and a disordered spinel
structure having a smaller lattice constant than a general regular
spinel structure is obtained. Therefore, when the tunnel barrier
layer includes two or more types of non-magnetic element having a
small ionic radius difference, the MR ratio further increases.
[0061] Oxygen atoms contained in the tunnel barrier layer 3 form
the A site tetra-coordinating with divalent cations, and form the B
site hexa-coordinating with trivalent cations. Oxygen atoms may be
vacant. Thus, in composition formula (1), y is a number that
satisfies 0<y.ltoreq.4. However, the tunnel barrier layer 3 may
have a portion in which y in composition formula (1) exceeds 4.
[0062] Among non-magnetic elements contained in the tunnel barrier
layer 3, gallium forms a B site of the spinel structure. When the B
site includes gallium and oxygen, since the symmetric MR ratio is
exhibited regardless of the sign of the bias voltage, the spin
polarizability hardly attenuates in a low bias region.
(Relationship Between Underlayer and Tunnel Barrier Layer)
[0063] A lattice constant difference between the underlayer 2 and
the tunnel barrier layer 3 is preferably small. That is, a
difference between a lattice constant of the crystal structure that
the underlayer 2 can have and a lattice constant of the tunnel
barrier layer 3 is preferably small. Specifically, selection is
performed such that a lattice mismatching degree defined in the
following formula is within 5%, and preferably within 3%.
lattice mismatching degree (%)=absolute value of
(C-nD)/nD.times.100
[0064] Here, C is a lattice constant of the tunnel barrier layer 3,
and D is a lattice constant of a crystal structure that the
underlayer 2 can have. n is a natural number or I/natural number,
and is generally 1, 1/2, or 2.
[0065] Here, the "crystal structure that the underlayer 2 can take"
means a crystal structure a bulk of TiN, VN, NbN, and TaN or a
mixed crystal thereof constituting the underlayer 2 and a crystal
structure expected to be (inherently) taken in the underlayer 2. As
described above, it is conceivable that the underlayer 2 is in an
intermediate condition between a perfect crystalline state and an
amorphous state. Therefore, what structure the crystal structure of
the underlayer 2 may have cannot be clearly defined. On the other
hand, it is not believed that the crystal structure of the actual
underlayer 2 is significantly different from the crystal structure
that can be taken when the underlayer 2 is constituted by a bulk
material. As the crystal structure that the underlayer 2 can
assume, there is a tetragonal crystal structure.
[0066] When a difference of lattice constants between the
underlayer 2 and the tunnel barrier layer 3 is small, the MR ratio
of the magnetoresistance effect element 100 increases. As described
above, the underlayer 2 formed by a reactive sputtering method is
thought to be amorphous. Therefore, the matching between the
crystal structure of the tunnel barrier layer 3 and the crystal
structure that the underlayer 2 can have an influence on an
increase in the MR ratio of the magnetoresistance effect element
100, which is a novel finding.
[0067] For example, when the tunnel barrier layer 3 is made of a
non-magnetic insulating material in which A in composition formula
(1) is a cation of at least one element selected from the group
consisting of magnesium and zinc, the underlayer 2 is preferably
made of one or more selected from the group consisting of TiN, VN,
and TaN, or mixed crystals thereof. In addition, when the tunnel
barrier layer 3 is made of a non-magnetic insulating material in
which A in composition formula (1) is a cadmium ion, the underlayer
2 is preferably made of NbN.
(First Ferromagnetic Metal Layer)
[0068] As a material of the first ferromagnetic metal layer 6, a
ferromagnetic material, and particularly a soft magnetic material
is applied. For example, a metal selected from the group consisting
of Cr, Mn, Co, Fe, and Ni, an alloy containing at least one metal
of the above group, and an alloy containing one or a plurality of
metals selected from the group and at least one element among B, C,
and N may be exemplified. Specifically, Co--Fe, Co--Fe--B, and
Ni--Fe can be exemplified.
[0069] When a magnetization direction of the first ferromagnetic
metal layer 6 is perpendicular to the lamination surface, the film
thickness of the first ferromagnetic metal layer 6 is preferably
2.5 nm or less. At the interface between the first ferromagnetic
metal layer 6 and the tunnel barrier layer 3, perpendicular
magnetic anisotropy can be applied to the first ferromagnetic metal
layer 6. In addition, since the effect of perpendicular magnetic
anisotropy is weakened when the film thickness of the first
ferromagnetic metal layer 6 increases, the film thickness of the
first ferromagnetic metal layer 6 is preferably small.
(Second Ferromagnetic Metal Layer)
[0070] As a material of the second ferromagnetic metal layer 7, for
example, a metal selected from the group consisting of Cr, Mn, Co,
Fe, and Ni, an alloy containing at least one metal of the above
group, and an alloy containing one or a plurality of metals
selected from the group and at least one element among B, C, and N
may be exemplified. Specifically, Co--Fe and Co--Fe--B can be
exemplified. Further, in order to obtain a high output, the Heusler
alloy such as Co.sub.2FeSi is preferable. The Heusler alloy
includes an intermetallic compound having the chemical composition
of X.sub.2YZ. X is a transition metal element of the group Co, Fe,
Ni, or Cu in the periodic table or a noble metal element. Y is a
transition metal of the group Mn, V, Cr, or Ti, and can also be an
element of type X. Z is a typical element of group III to group V.
For example, Co.sub.2FeSi, Co.sub.2MnSi, and
Co.sub.2Mn.sub.1-aFe.sub.aAl.sub.bSi.sub.1-b may be exemplified. In
addition, as a material in contact with the second ferromagnetic
metal layer 7, an antiferromagnetic material such as IrMn or PtMn
may be used in order for coercivity to be greater than that of the
first ferromagnetic metal layer 6. Further, in order to prevent a
leakage magnetic field of the second ferromagnetic metal layer 7
from influencing the first ferromagnetic metal layer 6, a synthetic
ferromagnetic coupling structure may be used.
[0071] When a magnetization direction of the second ferromagnetic
metal layer 7 is perpendicular to the lamination surface, a
laminate film of Co and Pt is preferably used. When the second
ferromagnetic metal layer 7 is formed of, for example, FeB (1.0
nm)/Ta (0.2 nm)/[Pt (0.16 nm)/Co (0.16 nm)].sub.4/Ru (0.9 nm)/[Co
(0.24 nm)/Pt (0.16 nm)].sub.6, the magnetization direction can be
set to perpendicular thereto.
[0072] In general, the first ferromagnetic metal layer 6 is called
a free layer because the magnetization direction can be more easily
changed due to an external magnetic field or spin torque than in
the second ferromagnetic metal layer 7. In addition, the second
ferromagnetic metal layer 7 has a structure in which the
magnetization direction is fixed, and the second ferromagnetic
metal layer 7 is called a fixed layer.
(Substrate)
[0073] The magnetoresistance effect element according to the
present invention may be formed on a substrate.
[0074] In this case, a material excellent in flatness is preferably
used for the substrate 1. The substrate 1 varies depending on
desired products. For example, in the case of an MRAM, a circuit
formed on an Si substrate can be used under a magnetoresistance
effect element. Alternatively, in the case of magnetic head, an
AlTiC substrate that is easily processed can be used.
(Cap Layer)
[0075] In the magnetoresistance effect element according to the
present invention, a cap layer may be formed on the surface (in
FIG. 1, an upper surface of the second ferromagnetic metal layer 7)
opposite to the side of the tunnel barrier layer 3 of the second
ferromagnetic metal layer 7.
[0076] The cap layer 4 is provided on the second ferromagnetic
metal layer 7 in the lamination direction and is used for
controlling crystallinity such as a crystal direction and a grain
size of the second ferromagnetic metal layer 7 and diffusion of
elements. When the crystal structure of the second ferromagnetic
metal layer 7 is the bcc structure, the crystal structure of the
cap layer 4 may be any one of the fcc structure, the hcp structure,
and the bcc structure. When the crystal structure of the second
ferromagnetic metal layer 7 is the fcc structure, the crystal
structure of the cap layer 4 may be any one of the fcc structure,
the hcp structure, and the bcc structure. The film thickness of the
cap layer 4 may be in a range in which a strain relaxation effect
is obtained and furthermore a reduction in the MR ratio due to a
shunt is not observed. The film thickness of the cap layer 4 is
preferably 1 nm or more and 30 nm or less.
(Shapes and Sizes of Elements)
[0077] The laminate including the first ferromagnetic metal layer
6, the tunnel barrier layer 3, and the second ferromagnetic metal
layer 7 constituting the present invention has a columnar shape.
The laminate in a plan view can have various shapes such as a
circle, a rectangle, a triangle, and a polygon, and is preferably
circular in consideration of the symmetry. That is, the laminate
preferably has a cylindrical shape.
[0078] When the laminate has a cylindrical shape, the diameter of
the circle in a plan view is preferably 80 nm or less, more
preferably 60 nm or less, and most preferably 30 nm or less.
[0079] When the diameter is 80 nm or less, it is difficult for the
ferromagnetic metal layer to have a domain structure, and it is not
necessary to take into account a component having spin polarization
different from that of the ferromagnetic metal layer. Further, when
the diameter is 30 nm or less, the ferromagnetic metal layer has a
single domain structure, and a magnetization reversal rate and a
probability increase. In addition, in a miniaturized
magnetoresistance effect element, in particular, there is a strong
demand for reducing the resistance.
(Configuration at the Time of Use)
[0080] FIG. 8 and FIG. 9 show examples of a magnetoresistance
effect device including the magnetoresistance effect element of the
present embodiment.
[0081] FIG. 8 is a plan view of a magnetoresistance effect device
200 (a diagram in which the magnetoresistance effect device 200 is
viewed from the above in a lamination direction). FIG. 9 is a
cross-sectional view taken along the line IX-IX in FIG. 8. In the
magnetoresistance effect device 200 shown in FIG. 8 and FIG. 9, an
electrode layer 5 that extends in the x direction is formed on the
cap layer 4 of the magnetoresistance effect element 100. The
underlayer 2 extends in the z direction past an end of the first
ferromagnetic metal layer 6, and an electrode pad 8 is formed above
the extended portion. Between the electrode layer 5 and the
electrode pad 8, a current source 71 and a voltmeter 72 are
provided. When voltage is applied to the underlayer 2 and the
electrode layer 5 by the current source 71, the current flows in
the lamination direction of the laminate including the first
ferromagnetic metal layer 6, the tunnel barrier layer 3, and the
second ferromagnetic metal layer 7. The applied voltage at this
time is monitored by the voltmeter 72.
(Evaluation Method)
[0082] An exemplary method of evaluating the magnetoresistance
effect element 100 will be described with reference to FIG. 8 and
FIG. 9. For example, as shown in FIG. 8, the current source 71 and
the voltmeter 72 are provided, constant current or constant voltage
is applied to the magnetoresistance effect element 100, and the
voltage or the current is measured while sweeping a magnetic field
from the outside. Thus, a change in the resistance of the
magnetoresistance effect element 100 can be observed.
[0083] The MR ratio is generally represented by the following
formula.
MR ratio (%)={(R.sub.AP-R.sub.P)/R.sub.P}.times.100
R.sub.P is a resistance when magnetization directions of the first
ferromagnetic metal layer 6 and the second ferromagnetic metal
layer 7 are parallel. R.sub.AP is a resistance when magnetization
directions of the first ferromagnetic metal layer 6 and the second
ferromagnetic metal layer 7 are antiparallel.
[0084] V.sub.half is obtained by measuring the MR ratio when a low
bias voltage of, for example, 1 mV is applied, and specifying a
voltage at which the MR ratio is reduced by half while increasing
the bias voltage. Here, when electrons move from the second
ferromagnetic metal layer 7 to the first ferromagnetic metal layer
6, V.sub.half is defined as a positive direction, and otherwise,
defined as a negative direction. That is, when a current flows from
the first ferromagnetic metal layer 6 to the second ferromagnetic
metal layer 7, this is set as a positive direction.
[0085] An area resistance (RA) is calculated by dividing a
resistance value obtained by dividing an applied bias voltage by a
current that flows in a lamination direction of the
magnetoresistance effect element by an area of a surface to which
layers are bonded, and is a normalized resistance value in a unit
area. An applied bias voltage and a value of a current that flows
in a lamination direction of the magnetoresistance effect element
can be obtained by measurement using a voltmeter and an
ammeter.
[0086] When a high current flows in the magnetoresistance effect
element 100, rotation of magnetization occurs due to an STT effect,
and a resistance value of the magnetoresistance effect element 100
sharply changes. A value of a current density at which the
resistance value sharply changes is called a reverse current
density (Jc)[A/cm.sup.2]. The reverse current density (Jc) can be
obtained when a current is caused to flow in the magnetoresistance
effect element 100 while gradually increasing a current value, a
resistance of the magnetoresistance effect element 100 is measured,
and a current value at which the resistance value sharply changes
is measured. Here, in the reverse current density (Jc), a flow of a
current from the first ferromagnetic metal layer 6 to the second
ferromagnetic metal layer 7 is defined as a positive direction.
(Others)
[0087] While an example of a structure in which the first
ferromagnetic metal layer 6 having a large coercivity is in a lower
position has been described in the present example, the present
invention is not limited to such a structure. A structure in which
the first ferromagnetic metal layer 6 having a large coercivity is
in an upper position has coercivity that is smaller than a
structure in which the first ferromagnetic metal layer 6 is in a
lower position. However, the tunnel barrier layer 3 can be formed
by utilizing crystallinity of the substrate so that it is possible
to increase the MR ratio.
[0088] In order to utilize the magnetoresistance effect element as
a magnetic sensor, a change in resistance with respect to an
external magnetic field is preferably linear. In a laminate film of
a general ferromagnetic layer, a magnetization direction is easily
directed into a lamination surface due to shape anisotropy. In this
case, for example, when a magnetic field is applied from the
outside and magnetization directions of the first ferromagnetic
metal layer and the second ferromagnetic metal layer are
perpendicular to each other, a change in resistance with respect to
the external magnetic field is linear. However, in this case, since
a mechanism for applying a magnetic field to the vicinity of the
magnetoresistance effect element is necessary, this is not
desirable for integration. When the ferromagnetic metal layer
itself has vertical magnetic anisotropy, a method of applying a
magnetic field from the outside is unnecessary, and this is
beneficial for integration.
[0089] The magnetoresistance effect element using the present
embodiment can be used as a magnetic sensor or a memory such as an
MRAM. In particular, the present embodiment is effective for
products that are used with a higher bias voltage than a bias
voltage used in the conventional magnetic sensor.
(Production Method)
[0090] The magnetoresistance effect element 100 can be formed
using, for example, a magnetron sputtering device.
[0091] The underlayer 2 can be produced according to a known
method, and for example, can be produced by a reactive sputtering
method using a mixed gas containing Ar and nitrogen as a sputtering
gas.
[0092] The tunnel barrier layer 3 can be produced according to a
known method. For example, a thin metal film is sputtered onto the
first ferromagnetic metal layer 6, natural oxidation occurs due to
plasma oxidation or oxygen introduction, and a subsequent heat
treatment is performed for formation. As a film formation method,
general thin film producing methods such as a vapor deposition
method, a laser ablation method, and an MBE method can be used in
addition to a magnetron sputtering method.
[0093] The first ferromagnetic metal layer 6, the second
ferromagnetic metal layer 7, and the cap layer 4 can be produced
according to a known method.
[0094] The underlayer 2, the first ferromagnetic metal layer 6, the
tunnel barrier layer 3, the second ferromagnetic metal layer 7, and
the cap layer 4 are formed as films in that order and laminated.
The obtained laminate film is preferably subjected to an annealing
treatment. A nitride layer (the underlayer 2) made of one or more
selected from the group consisting of TiN, VN, NbN, and TaN or,
mixed crystals thereof formed by the reactive sputtering method is
generally amorphous. The produced magnetoresistance effect element
100 that has undergone the annealing treatment has a higher MR
ratio than a produced magnetoresistance effect element 100 without
an annealing treatment. The reason for this is inferred to be as
follows. The underlayer 2 is partially crystallized due to the
annealing treatment, and thus uniformity and orientation of crystal
sizes of the tunnel barrier layer of the tunnel barrier layer 3 are
improved. As the annealing treatment, preferably, in an inert
atmosphere such as Ar, heating is performed at a temperature of
300.degree. C. or more and 500.degree. C. or less for a time of 5
minutes or longer and 100 minutes or shorter, and then, while a
magnetic field of 2 kOe or more and 10 kOe or less is applied,
heating is performed at a temperature of 100.degree. C. or more and
500.degree. C. or less for a time of 1 hour or longer and 10 hours
or shorter.
Second Embodiment
[0095] A difference between a second embodiment and the first
embodiment is only a method of forming a tunnel barrier layer. In
the first embodiment, the tunnel barrier layer is formed by
repeatedly performing formation of a metal film, oxidation,
formation of a metal film, and oxidation. In the second embodiment,
in the oxidation process, a temperature of the substrate is cooled
to -70 to -30.degree. C., and then oxidation is performed. When the
substrate is cooled, a temperature gradient occurs between the
substrate and a vacuum or between the substrate and plasma. First,
when oxygen is brought into contact with a surface of the
substrate, it reacts with a metal material and oxidation occurs.
However, since the temperature is low, oxidation does not proceed.
Accordingly, it is easy to adjust an amount of oxygen in the tunnel
barrier layer. In addition, when the temperature gradient is
formed, it is easy to adjust epitaxial growth (lattice-matched
growth). Since crystal growth proceeds according to the temperature
gradient, when the temperature of the substrate is sufficiently
cooled, epitaxial growth easily occurs. In addition, when the
temperature of the substrate increases, a plurality of crystal
nuclei are formed inside a surface in which a domain is formed, and
crystal nuclei grow independently epitaxially. Therefore, in a
portion in which crystal-grown domains are in contact with each
other, a portion in which lattices do not match is formed.
[0096] Preferably, a part of the tunnel barrier layer has a
lattice-matched portion that is lattice-matched with both of the
first ferromagnetic metal layer and the second ferromagnetic metal
layer. In general, the tunnel barrier layer that is completely
lattice-matched with both of the first ferromagnetic metal layer
and the second ferromagnetic metal layer is preferable.
[0097] However, when complete lattice matching occurs, since
electrons that are spin-polarized when they pass through the tunnel
barrier layer interfere with each other, hardly any pass through
the tunnel barrier layer. On the other hand, when a lattice-matched
portion in which lattice matching occurs partially exists,
interference of electrons spin-polarized when passing through the
tunnel barrier layer is appropriately cut in a portion in which no
lattice matching occurs, and the spin-polarized electrons easily
pass through the tunnel barrier layer. The volume ratio of the
lattice-matched portion in the tunnel barrier layer with respect to
the volume of the entire tunnel barrier layer is preferably 70 to
95%. When the volume ratio of the lattice-matched portion in the
tunnel barrier layer is less than 70%, since the coherent tunneling
effect is weakened, the MR ratio decreases. In addition, when the
volume ratio of the lattice-matched portion in the tunnel barrier
layer exceeds 95%, an effect of electrons spin-polarized when
passing through the tunnel barrier layer interfering with each
other is not weakened, and no improvement in effect of
spin-polarized electrons passing through the tunnel barrier layer
is observed.
(Method of Calculating Volume Ratio of Lattice-Matched Portion)
[0098] The volume ratio of the lattice-matched portion
(lattice-matched part) with respect to the volume of the entire
tunnel barrier layer can be estimated from, for example, a TEM
image. In order to determine whether lattice matching occurs, in a
cross-sectional TEM image, portions of the tunnel barrier layer,
the first ferromagnetic metal layer, and the second ferromagnetic
metal layer are subjected to Fourier transform, and an electron
beam diffraction image is obtained. In the electron beam
diffraction image obtained through Fourier transform, electron beam
diffraction places other than in a lamination direction are
removed. When this image is subjected to inverse Fourier transform,
an image including information about only the lamination direction
is obtained. In the lattice line in the inverse Fourier image, a
portion in which the tunnel barrier layer is continuously connected
to both of the first ferromagnetic metal layer and the second
ferromagnetic metal layer is set as a lattice-matched portion. In
addition, a portion in which the tunnel barrier layer is not
continuously connected to at least one of the first ferromagnetic
metal layer and the second ferromagnetic metal layer in the lattice
line, or no lattice line is detected is set as a
non-lattice-matched portion. Since the lattice-matched portion is
continuously connected from the first ferromagnetic metal layer to
the second ferromagnetic metal layer through the tunnel barrier
layer in the lattice line in the inverse Fourier image, a width
(L.sub.C) of the lattice-matched portion can be measured from the
TEM image. On the other hand, similarly, since the
non-lattice-matched portion is not continuously connected in the
lattice line in the inverse Fourier image, a width (L.sub.I) of the
non-lattice-matched portion can be measured from the TEM image.
When the width (L.sub.C) of the lattice-matched portion is used as
a numerator and a sum of the width (L.sub.C) of the lattice-matched
portion and the width (L.sub.I) of the non-lattice-matched portion
is used as a denominator, the volume ratio of the lattice-matched
portion with respect to the volume of the entire tunnel barrier
layer can be obtained. Here, the TEM image is a cross-sectional
image, but it includes information containing a depth. Thus, it can
be understood that a region estimated from the TEM image is
proportional to the volume.
[0099] FIG. 10 is an example of a portion in which a tunnel barrier
layer and a ferromagnetic metal layer are lattice-matched. FIG.
10(a) is an example of a high resolution cross-sectional TEM image.
FIG. 10(b) is an example of an image obtained by removing electron
beam diffraction spots other than a lamination direction in an
electron beam diffraction image and then performing inverse Fourier
transform. In FIG. 10(b), components perpendicular to the
lamination direction are removed, and lattice lines can be observed
in the lamination direction. It shows that the tunnel barrier layer
and the ferromagnetic metal layer are continuously connected
without interruption at the interface.
[0100] FIG. 11 is a schematic structure diagram of a cross section
having a direction parallel to a lamination direction of the tunnel
barrier layer 3.
[0101] As shown in FIG. 11, the size (width: L.sub.C) of a
lattice-matched portion of the tunnel barrier layer 3 in a
direction parallel to a film surface is preferably 30 nm or less in
any portion. Approximately, 30 nm is about 10 times a lattice
constant of a CoFe alloy which is a material of the first
ferromagnetic metal layer 6 and the second ferromagnetic metal
layer 7. It is thought that mutual interference of spin-polarized
electrons in a direction perpendicular to a tunneling direction
before and after coherent tunneling is strengthened to about 10
times the lattice constant for purpose.
EXAMPLES
Example 1
[0102] An example of a method of producing the magnetoresistance
effect element according to the first embodiment will be described
below. A film was formed on the substrate 1 on which a thermally
oxidized silicon film was provided using a magnetron sputtering
method. First, 10 nm of TiN was formed on an upper surface of the
substrate 1 as the underlayer 2. The underlayer 2 was formed by a
reactive sputtering method in which a Ti target was used as a
target and a mixed gas containing Ar and nitrogen (volume ratio
1:1) was used as a sputtering gas. Next, TiN of the underlayer 2
was polished to 4 nm by CMP. Further, 2 nm of FeB was formed on the
underlayer 2 as the first ferromagnetic metal layer 6.
[0103] Next, the tunnel barrier layer 3 was formed on the first
ferromagnetic metal layer 6. A method of forming the tunnel barrier
layer 3 will be described. A target having an MgGa.sub.2 alloy
composition was sputtered to form an MgGa.sub.2 film of 0.5 nm.
Then, the specimen was moved into an oxidation chamber maintained
at an ultra-high vacuum of 1.times.10.sup.-8 Pa or less, and Ar and
oxygen were introduced to cause natural oxidation. A time of
natural oxidation was 10 seconds, a partial pressure ratio between
Ar and oxygen was 1:25, and a total gas pressure was 0.05 Pa. Then,
the film was returned to a film forming chamber, and an MgGa.sub.2
film of 0.4 nm was formed. Further, the specimen was moved into an
oxidation chamber maintained at an ultra-high vacuum of
1.times.10.sup.-8 Pa or less, and Ar and oxygen were introduced to
cause natural oxidation and inductively coupled plasma oxidation. A
time of natural oxidation was 30 seconds, a time of inductively
coupled plasma oxidation was 5 seconds, and a partial pressure
ratio between Ar and oxygen was 1:20, and a total gas pressure was
0.08 Pa.
[0104] The laminate film was moved again to the film forming
chamber, and as the second ferromagnetic metal layer 7, FeB(1.0
nm)/Ta(0.2 nm)/[Pt(0.16 nm)/Co(0.16 nm)].sub.4/R (0.9 nm)/[Co(0.24
nm)/Pt(0.16 nm).sub.6] were sequentially formed. Further, as the
cap layer 4, Ru (3 nm)/Ta (5 nm) was formed.
[0105] The laminate film was provided in an annealing device,
treated with Ar at a temperature of 450.degree. C. for 10 minutes,
and then was treated at a temperature of 280.degree. C. for 6 hours
while applying 8 kOe.
[0106] Next, as shown in FIGS. 8 and 9, the magnetoresistance
effect device was produced. First, the electrode layer 5 was formed
on the cap layer 4. Next, a photoresist was formed using electron
beam lithography so that the electrode layer was rotated 90
degrees. A portion other than under the photoresist was scraped off
by an ion milling method, the thermally oxidized silicon film
serving as the substrate was exposed, and the shape of the
underlayer 2 was formed.
[0107] Further, in a constricted portion of the shape of the
underlayer, a photoresist was formed to have a cylindrical shape of
80 nm using electron beam lithography. A portion other than under
the photoresist was scraped off by an ion milling method and the
underlayer was exposed. Then, SiOx as an insulating layer was
formed in a portion scraped off by ion milling. The cylindrical
photoresist of 80 nm was removed here. In order that the
photoresist was not formed only in the electrode pad portion of
FIGS. 8 and 9, the insulating layer was removed by an ion milling
method and the underlayer was exposed. Then, Au was formed. The
electrode pad 8 served as a contact electrode with the underlayer
of the laminate film. Next, in order to obtain the electrode layer
in FIGS. 8 and 9, the shape was formed using the photoresist and an
ion milling method, and Au was formed. This served as a contact
electrode with the electrode layer of the laminate film.
[0108] Physical properties of the obtained magnetoresistance effect
element and the composition and the structure of the tunnel barrier
layer were evaluated as follows.
(Characteristics Evaluation)
[0109] According to the above evaluation method, the MR ratio,
V.sub.hw, the area resistance (RA), and the reverse current density
(Jc) of the obtained magnetoresistance effect elements were
measured. Here, the MR ratio was measured under a condition of a
bias voltage of 1 V.
(Composition Analysis of Tunnel Barrier Layer)
[0110] Composition analysis of the tunnel barrier layer was
performed using energy dispersive X-ray analysis (EDS).
[0111] The composition of the tunnel barrier layer was determined
by measuring a relative amount of divalent cations (Mg, Zn, Cd)
when a content (number of atoms) of Ga was 2. Here, a content of O
was measured. However, in general, even when an amount of O in an
oxide is outside a quantitative proportion, the crystal structure
can be maintained.
(Structural Analysis of Tunnel Barrier Layer)
[0112] As structure analysis of the tunnel barrier layer, the
crystal structure and the lattice constant were evaluated.
[0113] The crystal structure was evaluated using an electron beam
diffraction image using a transmission electron beam. When the
structure of the barrier layer was examined according to this
method, if there is no reflection from the {022} plane that appears
in the regular spinel structure, the barrier layer was assumed to
have a spinel structure (Sukenel structure) in which cubic cations
were disordered.
[0114] The lattice constant was evaluated using a 4-axis X-ray
diffractometer. When the lattice constant was evaluated, it was
difficult to determine the lattice constant with the film thickness
of the tunnel barrier layer of the example.
[0115] Therefore, in order to obtain the lattice constant of the
tunnel barrier layer, a substrate in which a tunnel barrier layer
(thickness of 100 nm) was formed on an Si substrate including a
thermal oxide film was used. The surface of the Si substrate
including a thermal oxide film was amorphous SiOx and the substrate
was hardly influenced by formation of the tunnel barrier layer.
[0116] In addition, the tunnel barrier layer (thickness of 100 nm)
had a film thickness at which an influence of lattice distortion
due to the substrate was sufficiently mitigated, and a film
thickness at which it was possible to obtain an X-ray intensity for
sufficient structural analysis.
Example 2
[0117] A magnetoresistance effect element was produced in the same
manner as in Example 1 except that 10 nm of VN was formed as the
underlayer 2, and physical properties of the obtained
magnetoresistance effect element, and the composition and the
structure of the tunnel barrier layer were evaluated. The
underlayer was formed by a reactive sputtering method in which a V
target was used as a target and a mixed gas containing Ar and
nitrogen (volume ratio 1:1) was used as a sputtering gas. Here, VN
of the underlayer 2 was polished to 4 nm by CMP.
Example 3
[0118] A magnetoresistance effect element was produced in the same
manner as in Example 1 except that 10 nm of TaN was formed as the
underlayer 2, and physical properties of the obtained
magnetoresistance effect element, and the composition and the
structure of the tunnel barrier layer were evaluated. The
underlayer was formed by a reactive sputtering method in which a Ta
target was used as a target and a mixed gas containing Ar and
nitrogen (volume ratio 1:1) was used as a sputtering gas. Here, TaN
of the underlayer 2 was polished to 4 nm by CMP.
Example 4
[0119] A magnetoresistance effect element was produced in the same
manner as in Example 1 except that the tunnel barrier layer 3 was
formed as follows, and physical properties of the obtained
magnetoresistance effect element, and the composition and the
structure of the tunnel barrier layer were evaluated.
[0120] A target having a ZnGa.sub.2 alloy composition was sputtered
to form a ZnGa.sub.2 film of 0.5 nm.
[0121] Then, the specimen was moved into an oxidation chamber
maintained at an ultra-high vacuum of 1.times.10.sup.-8 Pa or less,
and Ar and oxygen were introduced to cause natural oxidation. A
time of natural oxidation was 10 seconds, a partial pressure ratio
between Ar and oxygen was 1:25, and a total gas pressure was 0.05
Pa. Then, the film was returned to a film forming chamber, and a
ZnGa.sub.2 film of 0.4 nm was formed. Further, the specimen was
moved into an oxidation chamber maintained at an ultra-high vacuum
of 1.times.10.sup.-8 Pa or less, and Ar and oxygen were introduced
to cause natural oxidation and inductively coupled plasma
oxidation. A time of natural oxidation was 30 seconds, a time of
inductively coupled plasma oxidation was 5 seconds, and a partial
pressure ratio between Ar and oxygen was 1:20, and a total gas
pressure was 0.08 Pa.
Example 5
[0122] A magnetoresistance effect element was produced in the same
manner as in Example 1 except that the underlayer 2 and the tunnel
barrier layer 3 were formed as follows, and physical properties of
the obtained magnetoresistance effect element, and the composition
and the structure of the tunnel barrier layer were evaluated.
[0123] The underlayer 2 was formed as follows.
[0124] 10 nm of NbN was formed by a reactive sputtering method in
which an Nb target was used as a target, and a mixed gas containing
Ar and nitrogen (volume ratio 1:1) was used as a sputtering
gas.
[0125] Next, NbN of the underlayer 2 was polished to 4 nm by
CMP.
[0126] The tunnel barrier layer 3 was formed as follows.
[0127] A target having a CdGa.sub.2 alloy composition was sputtered
to form a CdGa.sub.2 film of 0.5 nm.
[0128] Then, the specimen was moved into an oxidation chamber
maintained at an ultra-high vacuum of 1.times.10.8 Pa or less, and
Ar and oxygen were introduced to cause natural oxidation. A time of
natural oxidation was 10 seconds, a partial pressure ratio between
Ar and oxygen was 1:25, and a total gas pressure was 0.05 Pa. Then,
the film was returned to a film forming chamber, and a CdGa.sub.2
film of 0.4 nm was formed. Further, the specimen was moved into an
oxidation chamber maintained at an ultra-high vacuum of
1.times.10.sup.-8 Pa or less, and Ar and oxygen were introduced to
cause natural oxidation and inductively coupled plasma oxidation. A
time of natural oxidation was 30 seconds, a time of inductively
coupled plasma oxidation was 5 seconds, and a partial pressure
ratio between Ar and oxygen was 1:20, and a total gas pressure was
0.08 Pa. Here, it was confirmed that all of the tunnel barrier
layer, the first ferromagnetic metal layer, and the second
ferromagnetic metal layer had directions of basic lattices that
matched and had a cubic-on-cubic structure.
Example 6
[0129] A magnetoresistance effect element was produced in the same
manner as in Example 1 except that the tunnel barrier layer 3 was
formed as follows, and physical properties of the obtained
magnetoresistance effect element, and the composition and the
structure of the tunnel barrier layer were evaluated.
[0130] A target having an Mg and Mg.sub.0.5Ga.sub.2 alloy
composition was sputtered to form an Mg (0.05
nm)/Mg.sub.0.5Ga.sub.2 (0.4 nm) film. Then, the specimen was moved
into an oxidation chamber maintained at an ultra-high vacuum of
1.times.10.sup.-8 Pa or less, and Ar and oxygen were introduced to
cause natural oxidation. A time of natural oxidation was 10
seconds, a partial pressure ratio between Ar and oxygen was 1:25,
and a total gas pressure was 0.05 Pa. Then, the film was returned
to a film forming chamber, and an Mg (0.05 nm)/Mg.sub.0.5Ga.sub.2
(0.4 nm) film was formed. Further, the specimen was moved into an
oxidation chamber maintained at an ultra-high vacuum of
1.times.10.sup.-8 Pa or less, and Ar and oxygen were introduced to
cause natural oxidation and inductively coupled plasma oxidation. A
time of natural oxidation was 30 seconds, a time of inductively
coupled plasma oxidation was 5 seconds, and a partial pressure
ratio between Ar and oxygen was 1:20, and a total gas pressure was
0.08 Pa.
Comparative Example 1
[0131] A magnetoresistance effect element was produced in the same
manner as in Example 1 except that 10 nm of Cu was formed as the
underlayer 2, and physical properties of the obtained
magnetoresistance effect element, and the composition and the
structure of the tunnel barrier layer were evaluated. The
underlayer was formed by a sputtering method in which a Cu target
was used as a target. Here, 20 nm of Cu was formed and then 10 nm
of Cu was formed by CMP.
Comparative Example 2
[0132] A magnetoresistance effect element was produced in the same
manner as in Example 1 except that 4 nm of ZrN was formed as the
underlayer 2, and physical properties of the obtained
magnetoresistance effect element, and the composition and the
structure of the tunnel barrier layer were evaluated. The
underlayer was formed by a reactive sputtering method in which a Zr
target was used as a target, and a mixed gas containing Ar and
nitrogen (volume ratio 1:1) was used as a sputtering gas.
Comparative Example 3
[0133] A magnetoresistance effect element was produced in the same
manner as in Example 4 except that 4 nm of ZrN was formed as the
underlayer 2, and physical properties of the obtained
magnetoresistance effect element, and the composition and the
structure of the tunnel barrier layer were evaluated. The
underlayer was formed by a reactive sputtering method in which a Zr
target was used as a target, and a mixed gas containing Ar and
nitrogen (volume ratio 1:1) was used as a sputtering gas.
Comparative Example 4
[0134] A magnetoresistance effect element was produced in the same
manner as in Example 5 except that 4 nm of ZrN was formed as the
underlayer 2, and physical properties of the obtained
magnetoresistance effect element, and the composition and the
structure of the tunnel barrier layer were evaluated. The
underlayer was formed by a reactive sputtering method in which a Zr
target was used as a target, and a mixed gas containing Ar and
nitrogen (volume ratio 1:1) was used as a sputtering gas.
Comparison of Examples with Comparative Examples
[0135] Table 1 shows compositions of layers of the
magnetoresistance effect elements produced in Examples 1 to 6 and
Comparative Examples 1 to 4, the lattice constant of the nitride
constituting the underlayer 2, the lattice constant of the compound
constituting the tunnel barrier layer 3, the lattice mismatching
degree of the underlayer 2 and the tunnel barrier layer 3, the MR
ratio, V.sub.half, RA, and Jc. Here, the lattice constant of the
nitride is a value at which the crystal structure is a tetragonal
structure (NaCl structure) and a space group is Fm-3m. The lattice
mismatching degree is a value calculated when n in the above
computation formula is set to 1. In addition, in V.sub.half and Jc,
a + (positive) value is that at which a current flows from the
first ferromagnetic metal layer 6 to the second ferromagnetic metal
layer 7. A - (negative) value is that at which a current flows from
the second ferromagnetic metal layer 7 to the first ferromagnetic
metal layer 6.
[0136] Here, all of the tunnel barrier layers 3 of the
magnetoresistance effect elements produced in Examples 1 to 6 and
Comparative Examples 2 to 4 had a disordered spinel structure
(Sukenel structure).
TABLE-US-00001 TABLE 1 First Tunnel barrier Second MR Underlayer
ferro- layer ferro- lattice ratio Lattice magnetic Lattice magnetic
mis- @1 Compo- constant metal Compo- constant metal Cap matching V
V.sub.half RA Jc sition (nm) layer sition (nm) layer layer degree
[%] [%] [V] [.OMEGA. .mu.m.sup.2] [A/cm.sup.2] Example 1 TiN 0.4241
FeB MgGa.sub.2O.sub.y 0.4142 FeB/Ta/[Pt/ Ru/Ta 2.3 72.3 +1, -1 0.58
6.9 .times. Co].sub.4/ 10.sup.8 Ru/[Co/Pt].sub.6 Example 2 VN
0.4135 FeB MgGa.sub.2O.sub.y 0.4142 FeB/Ta/[Pt/ Ru/Ta 0.2 80.1
+0.95, -0.95 0.55 4.7 .times. Co].sub.4/ 10.sup.8 Ru/[Co/Pt].sub.6
Example 5 TaN 0.4330 FeB MgGa.sub.2O.sub.y 0.4142 FeB/Ta/[Pt/ Ru/Ta
4.3 68 +1, -1 0.60 8.7 .times. Co].sub.4/ 10.sup.8 Ru/[Co/Pt].sub.6
Example 4 TiN 0.4241 FeB ZnGa.sub.2O.sub.y 0.4168 FeB/Ta/[Pt/ Ru/Ta
1.7 58.2 +1, -0.95 0.61 1.0 .times. Co].sub.4/ 10.sup.9
Ru/[Co/Pt].sub.6 Example 5 NbN 0.4391 FeB CdGa.sub.2O.sub.y 0.4308
FeB/Ta/[Pt/ Ru/Ta 1.9 55 +1, -1 0.63 5.1 .times. Co].sub.4/
10.sup.8 Ru/[Co/Pt].sub.6 Example 6 TiN 0.4241 FeB
Mg.sub.0.81Ga.sub.2O.sub.y 0.4097 FeB/Ta/[Pt/ Ru/Ta 3.4 75 +0.9,
-0.9 0.57 5.6 .times. Co].sub.4/ 10.sup.8 Ru/[Co/Pt].sub.6 Compar-
Cu 0.3615 FeB MgGa.sub.2O.sub.y 0.4142 FeB/Ta/[Pt/ Ru/Ta 14.6 61.4
0.8, -0.65 0.62 2.0 .times. ative Co].sub.4/ 10.sup.9 Example 1
Ru/[Co/Pt].sub.6 Compar- ZrN 0.4573 FeB MgGa.sub.2O.sub.y 0.4142
FeB/Ta/[Pt/ Ru/Ta 9.4 60.8 0.8, -0.65 0.63 1.9 .times. ative
Co].sub.4/ 10.sup.9 Example 2 Ru/[Co/Pt].sub.6 Compar- ZrN 0.4573
FeB ZnGa.sub.2O.sub.y 0.4168 FeB/Ta/[Pt/ Ru/Ta 8.9 49.2 0.9, -0.9
0.68 1.8 .times. ative Co].sub.4/ 10.sup.9 Example 3
Ru/[Co/Pt].sub.6 Compar- ZrN 0.4573 FeB CdGa.sub.2O.sub.y 0.4308
FeB/Ta/[Pt/ Ru/Ta 5.8 48.8 0.85, -0.85 0.65 1.8 .times. ative
Co].sub.4/ 10.sup.9 Example 4 Ru/[Co/Pt].sub.6
[0137] When comparing Examples 1 to 3 with Comparative Examples 1
and 2, comparing Example 4 with Comparative Example 3, and
comparing Example 5 with Comparative Example 4, it was found that
the magnetoresistance effect elements produced in the examples had
a high MR ratio and low RA and Jc. In addition, it was found that,
in all of the magnetoresistance effect elements produced in the
examples, V.sub.half had almost the same + and - values, and the
symmetry of the MR ratio with respect to the polarity of a bias
voltage was favorable. This is thought to be caused by the fact
that the magnetoresistance effect elements of Comparative Examples
1 to 4 had a lower lattice mismatching degree between the crystal
lattice constant of the material constituting the tunnel barrier
layer and the crystal lattice constant that a nitride constituting
the underlayer has than the magnetoresistance effect elements of
Examples 1 to 6.
[0138] In addition, it was found that the magnetoresistance effect
element of Example 6 in which the tunnel barrier layer had a
disordered spinel structure (Mg.sub.0.81Ga.sub.2O.sub.y) had a
higher MR ratio and a lower RA and Jc than the magnetoresistance
effect element of Example 1 having a regular spinel structure
(MgGa.sub.2O.sub.y).
[0139] Based on the results of the above examples, according to the
present invention, it was confirmed that it was possible to obtain
a magnetoresistance effect element which has favorable symmetry of
an MR ratio with respect to the polarity of a bias voltage and is
capable of efficiently reversing magnetization according to a
current, and has a high MR ratio.
[0140] While preferred embodiments of the invention have been
described and illustrated above, it should be understood that these
are exemplary of the invention and are not to be considered as
limiting. Additions, omissions, substitutions, and other
modifications can be made without departing from the spirit or
scope of the present invention. Accordingly, the invention is not
to be considered as being limited by the foregoing description, and
is only limited by the scope of the appended claims.
EXPLANATION OF REFERENCES
[0141] 100: Magnetoresistance effect element [0142] 200:
Magnetoresistance effect device [0143] 1: Substrate [0144] 2:
Underlayer [0145] 3: Tunnel barrier layer [0146] 4: Cap layer
[0147] 5: Electrode layer [0148] 6: First ferromagnetic metal layer
[0149] 7: Second ferromagnetic metal layer [0150] 8: Electrode pad
[0151] 71: Current source [0152] 72: Voltmeter
* * * * *
References